CA2624332A1 - High damping expandable material - Google Patents
High damping expandable material Download PDFInfo
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- CA2624332A1 CA2624332A1 CA002624332A CA2624332A CA2624332A1 CA 2624332 A1 CA2624332 A1 CA 2624332A1 CA 002624332 A CA002624332 A CA 002624332A CA 2624332 A CA2624332 A CA 2624332A CA 2624332 A1 CA2624332 A1 CA 2624332A1
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- Prior art keywords
- expandable material
- thermally expandable
- weight
- accordance
- styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D153/02—Vinyl aromatic monomers and conjugated dienes
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
- E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
- E04C2/02—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
- E04C2/26—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials composed of materials covered by two or more of groups E04C2/04, E04C2/08, E04C2/10 or of materials covered by one of these groups with a material not specified in one of the groups
- E04C2/284—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials composed of materials covered by two or more of groups E04C2/04, E04C2/08, E04C2/10 or of materials covered by one of these groups with a material not specified in one of the groups at least one of the materials being insulating
-
- G—PHYSICS
- G10—MUSICAL INSTRUMENTS; ACOUSTICS
- G10K—SOUND-PRODUCING DEVICES; METHODS OR DEVICES FOR PROTECTING AGAINST, OR FOR DAMPING, NOISE OR OTHER ACOUSTIC WAVES IN GENERAL; ACOUSTICS NOT OTHERWISE PROVIDED FOR
- G10K11/00—Methods or devices for transmitting, conducting or directing sound in general; Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
- G10K11/16—Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
Abstract
A thermally expandable material is provided that, once expanded, has a Young's storage modulus E' between 0.1 MPa and 1000 MPa, a loss factor of at least 0.3 (preferably, at least 1) and a shear storage modulus G' preferably between 0.1 MPa and 500 MPa at a temperature between -10 and +40 degrees C in the frequency range 0 to 500 Hz. Such materials are useful in connection with reducing the transfer of vibrations from a vibration generator, as may be present in a vehicle.
Description
HIGH DAMPING EXPANDABLE MATERIAL
FIELD OF THE INVENTION
The present invention relates to a thermally expandable material useful for adhesive, sealing and coating purposes that, when expanded, is particularly effective in reducing the transfer of vibrations generated by a vibration generator.
BACKGROUND OF THE INVENTION
In a vehicle, the transfer of vibrations generated by a dynamic force generator, such as an engine, a motor, a pump or a gear box, via structural elements to an emitting surface such as a paitel, leads to the emission of structure borne noise.
Different solutions have been suggested in order to at least reduce such structure borne noise. In vehicle construction, passive measures such as the recourse to vibration dampers or dampening mats have been proposed. Such dampening mats are often applied on vibrating panels, e.g., in the doors or on the floor of a vehicle. The extent of noise reduction of these methods is often unsatisfactory.
In the conventional process, mixtures of bitumen or asphalt and fillers with a high specific weight are extruded into sheets, from which the appropriate shapes are punched or cut. These sheets are then bonded to the appropriate metal sheet parts and must sometimes also be adapted to the shape of the sheet by heating. Although these bitumen sheets are still frequently used because of their low material cost, they are very brittle and tend to peel off from the metal sheet, particularly at low temperatures. Also, the incorporation of additives which has often been proposed only results in a slight improvement which is not sufficient for many applications.
Moreover, it is completely impossible to apply the pre-formed bitumen parts to the complex-shaped or almost inaccessible metal sheet parts of machines or vehicles, e.g., the inner surfaces of the cavities of motor vehicle doors. In addition, there is the further disadvantage that in many CONFIRMATION COPY
FIELD OF THE INVENTION
The present invention relates to a thermally expandable material useful for adhesive, sealing and coating purposes that, when expanded, is particularly effective in reducing the transfer of vibrations generated by a vibration generator.
BACKGROUND OF THE INVENTION
In a vehicle, the transfer of vibrations generated by a dynamic force generator, such as an engine, a motor, a pump or a gear box, via structural elements to an emitting surface such as a paitel, leads to the emission of structure borne noise.
Different solutions have been suggested in order to at least reduce such structure borne noise. In vehicle construction, passive measures such as the recourse to vibration dampers or dampening mats have been proposed. Such dampening mats are often applied on vibrating panels, e.g., in the doors or on the floor of a vehicle. The extent of noise reduction of these methods is often unsatisfactory.
In the conventional process, mixtures of bitumen or asphalt and fillers with a high specific weight are extruded into sheets, from which the appropriate shapes are punched or cut. These sheets are then bonded to the appropriate metal sheet parts and must sometimes also be adapted to the shape of the sheet by heating. Although these bitumen sheets are still frequently used because of their low material cost, they are very brittle and tend to peel off from the metal sheet, particularly at low temperatures. Also, the incorporation of additives which has often been proposed only results in a slight improvement which is not sufficient for many applications.
Moreover, it is completely impossible to apply the pre-formed bitumen parts to the complex-shaped or almost inaccessible metal sheet parts of machines or vehicles, e.g., the inner surfaces of the cavities of motor vehicle doors. In addition, there is the further disadvantage that in many CONFIRMATION COPY
cases several punched parts are required for only one vehicle or appliance and therefore costly storage is required.
There has consequently been no lack of attempts to eliminate the disadvantages of bitumen sheets using other polymer systems. For example, aqueous polymer dispersions of polyvinylacetate or ethylene-vinylacetate copolymers containing fillers were developed which can be sprayed on to the metal sheet parts with the necessary coating thickness. These systems are, however, disadvantageous for industrial use when there are high rates of production because the water cannot be removed rapidly enough from the coating that is sprayed on, particularly when this coating is fairly thick.
The sound damping properties of polymer coatings are best in the range of the glass transition temperature of the polymer system, because due to the viscoelasticity of the polymer in this temperature range the mechanical energy of the vibration process is converted into heat by molecular flow phenomena. Conventional sprayable coating materials based on PVC plastisols, which, e.g., are widely used as underbody coatings in motor vehicle construction, have no notable sound damping effect in the application temperature range of -20 to +60 C because the maximum value of the glass transition is about -20 C to - 50 C, depending on the proportion of plasticizer. Attempts were therefore made to modify these conventional PVC
plastisols so that they would have better sound damping properties in the application temperature range of -20 C
to +60 C. Coatings are known from German published patent application 3514753 which contain multiply unsaturated compounds, e.g., di- or triacrylates, peroxide cross-linking agents and inorganic fillers, in conventional PVC plastisols. In the hardened state, these plastisols are, however, glass-hard and brittle, and are therefore not really suitable for use in automobile construction because they do not have sufficient flexibility, particularly at low temperatures.
Apart from this, these formulations have a very low loss factor tan 6 and thus the sound damping effect is not very marked.
Compositions are described in German published patent application 3444863 which contain PVC
or vinylchloride/vinylacetate copolymers, optionally methylmethacrylate homopolymers or copolymers, a plasticizer mixture and inert fillers. The plasticizer mixture comprises plasticizers which are compatible with the methylmethacrylate polymers and plasticizers for the vinylchloride polymers which are incompatible with the methylmethacrylate polymers which may be present. The plastisols thus obtained have improved sound damping properties compared with conventional PVC plastisols. However, particularly at temperatures above about 30 C, the sound damping effect drops again. If an attempt is made to shift the range of the maximum loss factor tan S to higher temperatures by varying the relative quantities of the individual components, the cold flexibility of the coating drops very severely. A reduced cold flexibility is, however, precisely what is disadvantageous in vehicle construction. In addition, the loss factor decreases very severely at lower temperatures with these formulations. These plastisol compositions therefore have a sufficiently high loss factor only in a very narrow temperature range.
Furthermore, active measures for reducing structure borne noise have been developed. These measures usually employ sensors, signal processing, actuators, and power sources to counteract or effectively increase the dissipation of the vibration by producing corresponding forces or strains.
Although active control measures have been shown to effectively reduce structure borne noise, they require sophisticated technical equipment, especially with respect to signal processing and sensors. This does not only increase the costs, but also leads to an increased risk of breakdown.
Therefore, there is a need for economic means for effectively reducing structure borne noise in a system, especially in a vehicle.
It is therefore an object of the present invention to overcome the drawbacks of the prior art.
BRIEF SUMMARY OF THE INVENTION
The present invention provides an expandable material that, once expanded, has a Young's storage modulus E' between 0.1 MPa and 1000 MPa, a loss factor of at least 0.3 (preferably, at least 1) and preferably a shear storage modulus G' between 0.1 MPa and 500 MPa at a temperature between -10 and +40 degrees C in the frequency range 0 to 500 Hz.
This expandable material is useful in the manufacture of dissipative vibratory wave barriers as described in unpublished European Patent Application No. 05292082.4, filed 6 October 2005 (incorporated herein by reference in its entirety). Such barriers comprise a carrier having an inner surface and an outer surface, the carrier having a polygonal section, especially rectangular, optionally U-shaped and comprising on its outer surface a coating of the aforementioned expandable material.
DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS OF THE INVENTION
We have discovered that expandable materials that when expanded meet certain requirements with respect to Young's storage modulus (E'), loss factor and preferably also shear storage modulus (G') at a temperature between -10 and +40 degrees C in the frequency range 0 to 500 Hz are remarkably and unexpectedly efficient in controlling structure-borne vibrations.
Young's storage modulus (E') is defined as the ratio of tensile stress to tensile strain below the proportional limit of a material. Shear storage modulus G' is defined as the ratio of shearing stress to shearing strain within the proportional limit and is considered a measure of the equivalent energy stored elastically in a material. The loss factor (also sometimes referred to as the structural intrinsic damping or tan delta) is the ratio of the Young's loss modulus E" over Young's storage modulus E' for the damping in tension compression. For the damping in shear, the loss factor is the ratio of the shear loss modulus G" over the shear storage modulus G'.
These values may be readily determined by Dynamic Mechanical Analysis (DMA) of a material, which in the context of this invention is the thermally expandable material after expansion. As is well known in the art, Dynamic Mechanical Analysis can be performed either by an indirect method where the material is characterized on a carrier (Oberst's beam test) or by a direct method where the tested sample is made only from the material to be characterized (viscoanalyzer).
The thermally expandable material is a material that will foam and expand upon heating but that is typically solid (and preferably dimensionally stable) at room temperature (e.g., 15-30 degrees C). In some embodiments, the expandable material will be dry and non-tacky, but in other embodiments will be tacky. The thermally expandable material preferably is formulated such 5 that it is capable of being shaped or molded (e.g., by injection molding or extrusion) into the desired form for use, such shaping or molding being carried out at a temperature above room temperature that is sufficient to soften or melt the expandable material so that it can be readily processed but below the temperature at which expansion of the expandable material is induced.
Cooling the shaped or molded expandable material to room temperature yields a solid having the desired shape or form. Upon activation, i.e., upon being subjected to a temperature of between about 130 C and 240 C (depending on the exact formulation of expandable material that is used), the expandable material will typically expand to at least about 100% or at least about 150% or alternatively at least about 200% of its original volume. Even higher expansion rates (e.g., at least about 1000%) may be selected where required by the desired end use. When used in an automobile body, for example, the expandable material typically has an activation temperature lower than the temperature at which primer or paint is baked on the vehicle body during manufacture.
In an especially advantageous embodiment, the thermally expandable material comprises:
- from 25 to 70% by weight, preferably from 35 to 55% by weight, of at least one thermoplastic elastomer (preferably a styrene/butadiene or styrene/isoprene block copolymer or at least partially hydrogenated derivative thereof);
- from 15 to 40% by weight, preferably from 20 to 35% by weight, of at least one non-elastomeric thermoplastic (preferably an ethylene/vinyl acetate or ethylene/methyl acrylate copolymer);
- from 0.01 to 2% by weight, preferably from 0.05 to 1% by weight of at least one stabilizer or antioxidant;
- from 2 to 15% by weight of at least one blowing agent, preferably an amount effective to cause the expandable material to expand at least 100% in volume when heated at a temperature of 150 degrees C;
There has consequently been no lack of attempts to eliminate the disadvantages of bitumen sheets using other polymer systems. For example, aqueous polymer dispersions of polyvinylacetate or ethylene-vinylacetate copolymers containing fillers were developed which can be sprayed on to the metal sheet parts with the necessary coating thickness. These systems are, however, disadvantageous for industrial use when there are high rates of production because the water cannot be removed rapidly enough from the coating that is sprayed on, particularly when this coating is fairly thick.
The sound damping properties of polymer coatings are best in the range of the glass transition temperature of the polymer system, because due to the viscoelasticity of the polymer in this temperature range the mechanical energy of the vibration process is converted into heat by molecular flow phenomena. Conventional sprayable coating materials based on PVC plastisols, which, e.g., are widely used as underbody coatings in motor vehicle construction, have no notable sound damping effect in the application temperature range of -20 to +60 C because the maximum value of the glass transition is about -20 C to - 50 C, depending on the proportion of plasticizer. Attempts were therefore made to modify these conventional PVC
plastisols so that they would have better sound damping properties in the application temperature range of -20 C
to +60 C. Coatings are known from German published patent application 3514753 which contain multiply unsaturated compounds, e.g., di- or triacrylates, peroxide cross-linking agents and inorganic fillers, in conventional PVC plastisols. In the hardened state, these plastisols are, however, glass-hard and brittle, and are therefore not really suitable for use in automobile construction because they do not have sufficient flexibility, particularly at low temperatures.
Apart from this, these formulations have a very low loss factor tan 6 and thus the sound damping effect is not very marked.
Compositions are described in German published patent application 3444863 which contain PVC
or vinylchloride/vinylacetate copolymers, optionally methylmethacrylate homopolymers or copolymers, a plasticizer mixture and inert fillers. The plasticizer mixture comprises plasticizers which are compatible with the methylmethacrylate polymers and plasticizers for the vinylchloride polymers which are incompatible with the methylmethacrylate polymers which may be present. The plastisols thus obtained have improved sound damping properties compared with conventional PVC plastisols. However, particularly at temperatures above about 30 C, the sound damping effect drops again. If an attempt is made to shift the range of the maximum loss factor tan S to higher temperatures by varying the relative quantities of the individual components, the cold flexibility of the coating drops very severely. A reduced cold flexibility is, however, precisely what is disadvantageous in vehicle construction. In addition, the loss factor decreases very severely at lower temperatures with these formulations. These plastisol compositions therefore have a sufficiently high loss factor only in a very narrow temperature range.
Furthermore, active measures for reducing structure borne noise have been developed. These measures usually employ sensors, signal processing, actuators, and power sources to counteract or effectively increase the dissipation of the vibration by producing corresponding forces or strains.
Although active control measures have been shown to effectively reduce structure borne noise, they require sophisticated technical equipment, especially with respect to signal processing and sensors. This does not only increase the costs, but also leads to an increased risk of breakdown.
Therefore, there is a need for economic means for effectively reducing structure borne noise in a system, especially in a vehicle.
It is therefore an object of the present invention to overcome the drawbacks of the prior art.
BRIEF SUMMARY OF THE INVENTION
The present invention provides an expandable material that, once expanded, has a Young's storage modulus E' between 0.1 MPa and 1000 MPa, a loss factor of at least 0.3 (preferably, at least 1) and preferably a shear storage modulus G' between 0.1 MPa and 500 MPa at a temperature between -10 and +40 degrees C in the frequency range 0 to 500 Hz.
This expandable material is useful in the manufacture of dissipative vibratory wave barriers as described in unpublished European Patent Application No. 05292082.4, filed 6 October 2005 (incorporated herein by reference in its entirety). Such barriers comprise a carrier having an inner surface and an outer surface, the carrier having a polygonal section, especially rectangular, optionally U-shaped and comprising on its outer surface a coating of the aforementioned expandable material.
DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS OF THE INVENTION
We have discovered that expandable materials that when expanded meet certain requirements with respect to Young's storage modulus (E'), loss factor and preferably also shear storage modulus (G') at a temperature between -10 and +40 degrees C in the frequency range 0 to 500 Hz are remarkably and unexpectedly efficient in controlling structure-borne vibrations.
Young's storage modulus (E') is defined as the ratio of tensile stress to tensile strain below the proportional limit of a material. Shear storage modulus G' is defined as the ratio of shearing stress to shearing strain within the proportional limit and is considered a measure of the equivalent energy stored elastically in a material. The loss factor (also sometimes referred to as the structural intrinsic damping or tan delta) is the ratio of the Young's loss modulus E" over Young's storage modulus E' for the damping in tension compression. For the damping in shear, the loss factor is the ratio of the shear loss modulus G" over the shear storage modulus G'.
These values may be readily determined by Dynamic Mechanical Analysis (DMA) of a material, which in the context of this invention is the thermally expandable material after expansion. As is well known in the art, Dynamic Mechanical Analysis can be performed either by an indirect method where the material is characterized on a carrier (Oberst's beam test) or by a direct method where the tested sample is made only from the material to be characterized (viscoanalyzer).
The thermally expandable material is a material that will foam and expand upon heating but that is typically solid (and preferably dimensionally stable) at room temperature (e.g., 15-30 degrees C). In some embodiments, the expandable material will be dry and non-tacky, but in other embodiments will be tacky. The thermally expandable material preferably is formulated such 5 that it is capable of being shaped or molded (e.g., by injection molding or extrusion) into the desired form for use, such shaping or molding being carried out at a temperature above room temperature that is sufficient to soften or melt the expandable material so that it can be readily processed but below the temperature at which expansion of the expandable material is induced.
Cooling the shaped or molded expandable material to room temperature yields a solid having the desired shape or form. Upon activation, i.e., upon being subjected to a temperature of between about 130 C and 240 C (depending on the exact formulation of expandable material that is used), the expandable material will typically expand to at least about 100% or at least about 150% or alternatively at least about 200% of its original volume. Even higher expansion rates (e.g., at least about 1000%) may be selected where required by the desired end use. When used in an automobile body, for example, the expandable material typically has an activation temperature lower than the temperature at which primer or paint is baked on the vehicle body during manufacture.
In an especially advantageous embodiment, the thermally expandable material comprises:
- from 25 to 70% by weight, preferably from 35 to 55% by weight, of at least one thermoplastic elastomer (preferably a styrene/butadiene or styrene/isoprene block copolymer or at least partially hydrogenated derivative thereof);
- from 15 to 40% by weight, preferably from 20 to 35% by weight, of at least one non-elastomeric thermoplastic (preferably an ethylene/vinyl acetate or ethylene/methyl acrylate copolymer);
- from 0.01 to 2% by weight, preferably from 0.05 to 1% by weight of at least one stabilizer or antioxidant;
- from 2 to 15% by weight of at least one blowing agent, preferably an amount effective to cause the expandable material to expand at least 100% in volume when heated at a temperature of 150 degrees C;
- from 0.5 to 4% by weight of one or more curing agents, optionally including from 0.5 to 2%
by weight of at least one olefinically unsaturated monomer or oligomer, and optionally - up to 10% by weight (e.g., 0.1 to 10% by weight) of at least one tackifying resin;
- up to 5% by weight (e.g., 0.1 to 5% by weight) of at least one plasticizer;
- up to 10% by weight (e.g., 0.1 to 10% by weight) of at least one wax;
- up to 3% by weight (e.g., 0.05 to 3% by weight) of at least one activator for the blowing agent;
as well as optionally at least one filler (although the amount of filler is preferably less than 10%
by weight, more preferably less than 5% by weight), the percentages being expressed as weight percentages of the total weight of the thermally expandable material.
Generally speaking, it will be desirable to use a thermoplastic elastomer that has a softening point no higher than the temperature at which the blowing agent begins to be activated, preferably at least about 30 degrees C lower than the temperature that the expandable material will be exposed to when it is to be expanded. The thermoplastic elastomer is preferably selected within the group consisting of thermoplastic polyurethanes (TPU) and block copolymers (including linear as well as radial block copolymers) of the A-B, A-B-A, A-(B-A)õ_2-B, A-(B-A)õ_, and (A-B)õY types, wherein A is an aromatic polyvinyl ("hard") block and the B block represents a rubber-like ("soft") block of polybutadiene, polyisoprene or the like, which may be partly or completely hydrogenated, Y is a polyfunctional compound and n is an integer of at least 3. The blocks may be tapered or gradient in character or consist entirely of one type of polymerized monomer.
Hydrogenation of the B block removes originally present double bonds and increases the thermal stability of the block copolymer. Such copolymers may be preferred in certain embodiments of the present invention.
Suitable block copolymers include, but are not limited to, SBS
(styrene/butadiene/styrene) copolymers, SIS (styrene/isoprene/styrene) copolymers, SEPS
(styrene/ethylene/propylene/styrene) copolymers, SEEPS (styrene/
ethylene/ethylene/propylene/styrene) or SEBS
(styrene/ethylene/butadiene/styrene) copolymers.
by weight of at least one olefinically unsaturated monomer or oligomer, and optionally - up to 10% by weight (e.g., 0.1 to 10% by weight) of at least one tackifying resin;
- up to 5% by weight (e.g., 0.1 to 5% by weight) of at least one plasticizer;
- up to 10% by weight (e.g., 0.1 to 10% by weight) of at least one wax;
- up to 3% by weight (e.g., 0.05 to 3% by weight) of at least one activator for the blowing agent;
as well as optionally at least one filler (although the amount of filler is preferably less than 10%
by weight, more preferably less than 5% by weight), the percentages being expressed as weight percentages of the total weight of the thermally expandable material.
Generally speaking, it will be desirable to use a thermoplastic elastomer that has a softening point no higher than the temperature at which the blowing agent begins to be activated, preferably at least about 30 degrees C lower than the temperature that the expandable material will be exposed to when it is to be expanded. The thermoplastic elastomer is preferably selected within the group consisting of thermoplastic polyurethanes (TPU) and block copolymers (including linear as well as radial block copolymers) of the A-B, A-B-A, A-(B-A)õ_2-B, A-(B-A)õ_, and (A-B)õY types, wherein A is an aromatic polyvinyl ("hard") block and the B block represents a rubber-like ("soft") block of polybutadiene, polyisoprene or the like, which may be partly or completely hydrogenated, Y is a polyfunctional compound and n is an integer of at least 3. The blocks may be tapered or gradient in character or consist entirely of one type of polymerized monomer.
Hydrogenation of the B block removes originally present double bonds and increases the thermal stability of the block copolymer. Such copolymers may be preferred in certain embodiments of the present invention.
Suitable block copolymers include, but are not limited to, SBS
(styrene/butadiene/styrene) copolymers, SIS (styrene/isoprene/styrene) copolymers, SEPS
(styrene/ethylene/propylene/styrene) copolymers, SEEPS (styrene/
ethylene/ethylene/propylene/styrene) or SEBS
(styrene/ethylene/butadiene/styrene) copolymers.
Especially suitable block copolymers include styrene/isoprene/styrene triblock polymers, as well as fully or partially hydrogenated derivatives thereof, in which the polyisoprene block contains a relatively high proportion of monomer moieties derived from isoprene having a 1,2 and/or 3,4 configuration. Preferably, at least about 50% of the polymerized isoprene monomer moieties have 1,2 and/or 3,4 configurations, with the remainder of the isoprene moieties having a 1,4 configuration. Such block copolymers are available from Kuraray Co., Ltd.
under the trademark HYBRAR and may also be prepared using the methods described in U.S. Pat. No.
4,987,194, incorporated herein by reference in its entirety.
In certain preferred embodiments of the invention the "hard" blocks represent from about 15 to about 30 percent by weight of the block copolymer and the "soft" blocks represent from about 70 to about 85 percent by weight of the block copolymer. The glass transition temperature of the "soft" blocks is preferably from about -35 degrees C to about 10 degrees C
while the glass transition temperature of the "hard" blocks is preferably from about 90 degrees C to about 110 degrees C. The melt flow index of the block copolymer preferably is from about 0.5 to about 6 (as measured by ASTM D1238, 190 degrees C, 2.16 Kg). Typically, the block copolymer will have a number average molecular weight of from about 30,000 to about 300,000.
Examples of suitable thermoplastic polyurethanes (TPU) are those made according to conventional processes by reacting diisocyanates with compositions having at least two isocyanate reactive groups per molecule, preferably difunctional alcohols.
Suitable organic diisocyanates to be used include, for example, aliphatic, cycloaliphatic, araliphatic, heterocyclic and aromatic diisocyanates.
Specific examples of diisocyanates include aliphatic diisocyanates such as, for example, hexamethylene-diisocyanate; cycloaliphatic diisocyanates such as, for example, isophorone-diisocyanate, 1,4-cyclohexane-diisocyanate, 1-methyl-2,4- and -2,6-cyclohexane-diisocyanate and the corresponding isomer mixtures, 4, 4-, 2, 4'- and 2,2'-dicyclohexylmethane-diisocyanate and the corresponding isomer mixtures; and aromatic diisocyanates such as, for example, 2,4-toluylene-diisocyanate, mixtures of 2,4- and 2,6-toluylene- diisocyanate, 4,4'-diphenylmethane-diisocyanate, 2,4'-diphenylmethane- diisocyanate and 2,2'-diphenylmethane-diisocyanate, mixtures of 2,4'- diphenylmethane- diisocyanate and 4,4'-diphenylmethane-diisocyanate, urethane-modified liquid 4,4'-diphenylmethane-diisocyanates and/or 2,4'-diphenylmethane-diisocyanates, 4,4'-diisocyanato- 1,2-diphenyl-ethane and 1,5-naphthylene-diisocyanate.
Diphenylmethane-diisocyanate isomer mixtures with a 4,4'- diphenylmethane-diisocyanate content of greater than 96 wt. % are preferably used, and 4,4'-diphenylmethane-diisocyanate and 1,5- naphthylene-diisocyanate are used in particular. The diisocyanates mentioned above can be used individually or in the form of mixtures with one another.
The compounds reactive with the isocyanate groups include, but are not limited to, polyhydroxy compounds such as polyester polyols, polyether polyols or polycarbonate-polyols or polyols which may contain nitrogen, phosphorus, sulfur and/or silicon atoms, or mixtures of these.
Linear hydroxyl-terminated polyols having on average from about 1.8 to about 3.0 Zerewitinoff-active hydrogen atoms per molecule, preferably from about 1.8 to about 2.2 Zerewitinoff-active hydrogen atoms per molecule, and having a number average molecular weight of 400 to 20,000 g/mol are preferably employed as polyol . These linear polyols often contain small amounts of non-linear compounds as a result of their production. Thus, these are also often referred to as "substantially linear polyols".
The polyhydroxy compounds with two or three hydroxyl groups per molecule in the number average molecular weight range of 400 to 20,000, preferably in the range of 1000 to 6000, which are liquid at room temperature, glassy solid/amorphous or crystalline, are preferably suitable as polyols. Examples are di- and/or trifunctional polypropylene glycols; random and/or block copolymers of ethylene oxide and propylene oxide can also be used. Another group of polyethers that can preferably be used includes the polytetramethylene glycols (poly(oxytetramethylene) glycol, poly-THF), which are produced, e.g., by the acid polymerization of tetrahydrofuran, the number average molecular weight range of these polytetramethylene glycols typically lying between 600 and 6000, preferably in the range of 800 to 5000.
The liquid, glassy amorphous or crystalline polyesters that can be produced by condensation of di- or tricarboxylic acids, such as, e.g., adipic acid, sebacic acid, glutaric acid, azelaic acid, suberic acid, undecanedioic acid, dodecanedioic acid, 3,3-dimethylglutaric acid, terephthalic acid, isophthalic acid, hexahydrophthalic acid, dimerized fatty acid or mixtures thereof with low molecular-weight diols or triols, such as e.g. ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, dimerized fatty alcohols, glycerin, trimethylolpropane or mixtures thereof, are also suitable as polyols.
Another group of polyols to be used for making the TPU's are polyesters based on E-caprolactone, also known as "polycaprolactones".
However, polyester polyols of oleochemical origin can also be used. These polyester polyols can be produced, for example, by the complete ring opening of epoxidized triglycerides of an at least partially olefinically unsaturated, fatty acid-containing fat mixture with one or more alcohols with 1 to 12 C atoms and subsequent partial transesterification of the triglyceride derivatives to alkyl ester polyols with 1 to 12 C atoms in the alkyl radical. Other suitable polyols are polycarbonate polyols and dimerized diols (Henkel), as well as castor oil and its derivatives. The hydroxyfunctional polybutadienes, as obtainable, for example, with the trade name "Poly-bd", can be used as polyols for making the TPU's to be used according to the invention.
Preferably, combinations of polyether polyols and glassy amorphous or crystalline polyester polyols are used for making the TPU's.
Preferably, the polyols have an average functionality towards isocyanate from about 1.8 to 2.3, preferably 1.9 to 2.2, particularly about 2Ø
The thermoplastic polyurethanes may also be made by additionally using chain extending compounds like low molecular weight polyols such as ethylene glycol, propylene glycol or butadiene glycol or low molecular weight diamines such as 1,2-diaminoethylene, 1,3-diaminopropylene or 1,4-diaminobutane or 1,6-diaminohexane.
In preferred embodiments, the soft domains of the thermoplastic polyurethane are selected from the group consisting of poly(ethylene adipate), poly(1,4-butene adipate), poly(ethylene 1,4-butene adipate), poly(hexamethylene 2,2-dimethylpropylene adipate), polycaprolactone, poly(diethylene glycol adipate), poly(1,6-hexanediol carbonate) and poly(oxytetramethylene).
Other thermoplastic elastomers suitable for use in the present invention include other types of block copolymers containing both hard segments and soft segments such as, for example, polystyrene/polydimethylsiloxane block copolymers, polysulfone/polydimethylsiloxane block copolymers, polyester/polyether block copolymers (e.g., copolyesters such as those synthesized 5 from dimethyl terephthalate, poly(tetramethylene ether) glycol, and tetramethylene glycol), polycarbonate/polydimethylsiloxane block copolymers, polycarbonate/polyether block copolymers, copolyetheramides, copolyetheresteramides and the like.
Thermoplastic elastomers which are not block copolymers but which generally are finely interdispersed multiphase systems or alloys may also be used, including blends of polypropylene with ethylene-propylene rubbers 10 (EPR) or ethylene-propylene-diene monomer (EPDM) rubbers (such blends often being grafted or cross-linked).
In addition to one or more thermoplastic elastomers, it is also preferred for the expandable material to contain one or more non-elastomeric thermoplastics. Preferably, the non-elastomeric thermoplastic is selected so as to improve the adhesion properties and processability of the expandable material. Generally speaking, it will be desirable to use a non-elastomeric thermoplastic that has a softening point no higher than the temperature at which the blowing agent begins to be activated, preferably at least about 30 degrees C lower than the temperature that the expandable material will be exposed to when such material is to be expanded.
Particularly preferred non-elastomeric thermoplastics include olefin polymers, especially copolymers of olefins (e.g., ethylene) with non-olefinic monomers (e.g., vinyl esters such as vinyl acetate and vinyl propionate, (meth)acrylate esters such as Cl to C6 alkyl esters of acrylic acid and methacrylic acid). Exemplary non-elastomeric thermoplastics especially suitable for use in the present invention include ethylene/vinyl acetate copolymers (particularly copolymers containing from about 20 to about 35 weight % vinyl acetate) and ethylene/methyl acrylate copolymers (particularly copolymers containing from about 15 to about 35 weight % methyl acrylate and/or having Vicat softening points less than 50 degrees C and/or melting points within the range of 60 to 80 degrees C and/or melt flow indices of from 3 to 25 g/10 minutes, as measured by ASTM D1238, 190 degrees C, 2.16 Kg).
In certain embodiments of the invention, the weight ratio of thermoplastic elastomer: non-elastomeric thermoplastic is at least 0.5:1 or at least 1:1 and/or not greater than 5:1 or 2.5:1.
under the trademark HYBRAR and may also be prepared using the methods described in U.S. Pat. No.
4,987,194, incorporated herein by reference in its entirety.
In certain preferred embodiments of the invention the "hard" blocks represent from about 15 to about 30 percent by weight of the block copolymer and the "soft" blocks represent from about 70 to about 85 percent by weight of the block copolymer. The glass transition temperature of the "soft" blocks is preferably from about -35 degrees C to about 10 degrees C
while the glass transition temperature of the "hard" blocks is preferably from about 90 degrees C to about 110 degrees C. The melt flow index of the block copolymer preferably is from about 0.5 to about 6 (as measured by ASTM D1238, 190 degrees C, 2.16 Kg). Typically, the block copolymer will have a number average molecular weight of from about 30,000 to about 300,000.
Examples of suitable thermoplastic polyurethanes (TPU) are those made according to conventional processes by reacting diisocyanates with compositions having at least two isocyanate reactive groups per molecule, preferably difunctional alcohols.
Suitable organic diisocyanates to be used include, for example, aliphatic, cycloaliphatic, araliphatic, heterocyclic and aromatic diisocyanates.
Specific examples of diisocyanates include aliphatic diisocyanates such as, for example, hexamethylene-diisocyanate; cycloaliphatic diisocyanates such as, for example, isophorone-diisocyanate, 1,4-cyclohexane-diisocyanate, 1-methyl-2,4- and -2,6-cyclohexane-diisocyanate and the corresponding isomer mixtures, 4, 4-, 2, 4'- and 2,2'-dicyclohexylmethane-diisocyanate and the corresponding isomer mixtures; and aromatic diisocyanates such as, for example, 2,4-toluylene-diisocyanate, mixtures of 2,4- and 2,6-toluylene- diisocyanate, 4,4'-diphenylmethane-diisocyanate, 2,4'-diphenylmethane- diisocyanate and 2,2'-diphenylmethane-diisocyanate, mixtures of 2,4'- diphenylmethane- diisocyanate and 4,4'-diphenylmethane-diisocyanate, urethane-modified liquid 4,4'-diphenylmethane-diisocyanates and/or 2,4'-diphenylmethane-diisocyanates, 4,4'-diisocyanato- 1,2-diphenyl-ethane and 1,5-naphthylene-diisocyanate.
Diphenylmethane-diisocyanate isomer mixtures with a 4,4'- diphenylmethane-diisocyanate content of greater than 96 wt. % are preferably used, and 4,4'-diphenylmethane-diisocyanate and 1,5- naphthylene-diisocyanate are used in particular. The diisocyanates mentioned above can be used individually or in the form of mixtures with one another.
The compounds reactive with the isocyanate groups include, but are not limited to, polyhydroxy compounds such as polyester polyols, polyether polyols or polycarbonate-polyols or polyols which may contain nitrogen, phosphorus, sulfur and/or silicon atoms, or mixtures of these.
Linear hydroxyl-terminated polyols having on average from about 1.8 to about 3.0 Zerewitinoff-active hydrogen atoms per molecule, preferably from about 1.8 to about 2.2 Zerewitinoff-active hydrogen atoms per molecule, and having a number average molecular weight of 400 to 20,000 g/mol are preferably employed as polyol . These linear polyols often contain small amounts of non-linear compounds as a result of their production. Thus, these are also often referred to as "substantially linear polyols".
The polyhydroxy compounds with two or three hydroxyl groups per molecule in the number average molecular weight range of 400 to 20,000, preferably in the range of 1000 to 6000, which are liquid at room temperature, glassy solid/amorphous or crystalline, are preferably suitable as polyols. Examples are di- and/or trifunctional polypropylene glycols; random and/or block copolymers of ethylene oxide and propylene oxide can also be used. Another group of polyethers that can preferably be used includes the polytetramethylene glycols (poly(oxytetramethylene) glycol, poly-THF), which are produced, e.g., by the acid polymerization of tetrahydrofuran, the number average molecular weight range of these polytetramethylene glycols typically lying between 600 and 6000, preferably in the range of 800 to 5000.
The liquid, glassy amorphous or crystalline polyesters that can be produced by condensation of di- or tricarboxylic acids, such as, e.g., adipic acid, sebacic acid, glutaric acid, azelaic acid, suberic acid, undecanedioic acid, dodecanedioic acid, 3,3-dimethylglutaric acid, terephthalic acid, isophthalic acid, hexahydrophthalic acid, dimerized fatty acid or mixtures thereof with low molecular-weight diols or triols, such as e.g. ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, dimerized fatty alcohols, glycerin, trimethylolpropane or mixtures thereof, are also suitable as polyols.
Another group of polyols to be used for making the TPU's are polyesters based on E-caprolactone, also known as "polycaprolactones".
However, polyester polyols of oleochemical origin can also be used. These polyester polyols can be produced, for example, by the complete ring opening of epoxidized triglycerides of an at least partially olefinically unsaturated, fatty acid-containing fat mixture with one or more alcohols with 1 to 12 C atoms and subsequent partial transesterification of the triglyceride derivatives to alkyl ester polyols with 1 to 12 C atoms in the alkyl radical. Other suitable polyols are polycarbonate polyols and dimerized diols (Henkel), as well as castor oil and its derivatives. The hydroxyfunctional polybutadienes, as obtainable, for example, with the trade name "Poly-bd", can be used as polyols for making the TPU's to be used according to the invention.
Preferably, combinations of polyether polyols and glassy amorphous or crystalline polyester polyols are used for making the TPU's.
Preferably, the polyols have an average functionality towards isocyanate from about 1.8 to 2.3, preferably 1.9 to 2.2, particularly about 2Ø
The thermoplastic polyurethanes may also be made by additionally using chain extending compounds like low molecular weight polyols such as ethylene glycol, propylene glycol or butadiene glycol or low molecular weight diamines such as 1,2-diaminoethylene, 1,3-diaminopropylene or 1,4-diaminobutane or 1,6-diaminohexane.
In preferred embodiments, the soft domains of the thermoplastic polyurethane are selected from the group consisting of poly(ethylene adipate), poly(1,4-butene adipate), poly(ethylene 1,4-butene adipate), poly(hexamethylene 2,2-dimethylpropylene adipate), polycaprolactone, poly(diethylene glycol adipate), poly(1,6-hexanediol carbonate) and poly(oxytetramethylene).
Other thermoplastic elastomers suitable for use in the present invention include other types of block copolymers containing both hard segments and soft segments such as, for example, polystyrene/polydimethylsiloxane block copolymers, polysulfone/polydimethylsiloxane block copolymers, polyester/polyether block copolymers (e.g., copolyesters such as those synthesized 5 from dimethyl terephthalate, poly(tetramethylene ether) glycol, and tetramethylene glycol), polycarbonate/polydimethylsiloxane block copolymers, polycarbonate/polyether block copolymers, copolyetheramides, copolyetheresteramides and the like.
Thermoplastic elastomers which are not block copolymers but which generally are finely interdispersed multiphase systems or alloys may also be used, including blends of polypropylene with ethylene-propylene rubbers 10 (EPR) or ethylene-propylene-diene monomer (EPDM) rubbers (such blends often being grafted or cross-linked).
In addition to one or more thermoplastic elastomers, it is also preferred for the expandable material to contain one or more non-elastomeric thermoplastics. Preferably, the non-elastomeric thermoplastic is selected so as to improve the adhesion properties and processability of the expandable material. Generally speaking, it will be desirable to use a non-elastomeric thermoplastic that has a softening point no higher than the temperature at which the blowing agent begins to be activated, preferably at least about 30 degrees C lower than the temperature that the expandable material will be exposed to when such material is to be expanded.
Particularly preferred non-elastomeric thermoplastics include olefin polymers, especially copolymers of olefins (e.g., ethylene) with non-olefinic monomers (e.g., vinyl esters such as vinyl acetate and vinyl propionate, (meth)acrylate esters such as Cl to C6 alkyl esters of acrylic acid and methacrylic acid). Exemplary non-elastomeric thermoplastics especially suitable for use in the present invention include ethylene/vinyl acetate copolymers (particularly copolymers containing from about 20 to about 35 weight % vinyl acetate) and ethylene/methyl acrylate copolymers (particularly copolymers containing from about 15 to about 35 weight % methyl acrylate and/or having Vicat softening points less than 50 degrees C and/or melting points within the range of 60 to 80 degrees C and/or melt flow indices of from 3 to 25 g/10 minutes, as measured by ASTM D1238, 190 degrees C, 2.16 Kg).
In certain embodiments of the invention, the weight ratio of thermoplastic elastomer: non-elastomeric thermoplastic is at least 0.5:1 or at least 1:1 and/or not greater than 5:1 or 2.5:1.
The tackifying resin may be selected within the group consisting of rosin resins, terpene resins, terpene phenolic resins, hydrocarbon resins derived from cracked petroleum distillates, aromatic tackifying resins, tall oil resins, ketone resins and aldehyde resins.
Suitable rosin resins are abietic acid, levopimaric acid, neoabietic acid, dextropimaric acid, palustric acid, alkyl esters of the aforementioned rosin acids, and hydrogenation products of rosin acid derivatives.
Examples of suitable plasticizers include CI_10 alkyl esters of dibasic acids (e.g., phthalate esters), diaryl ethers, benzoates of polyalkylene glycols, organic phosphates, and alkylsulfonic acid esters of phenol or cresol.
Suitable waxes include paraffinic waxes having melting ranges from 45 to 70 C, microcrystalline waxes with melting ranges from 60 to 95 C, synthetic Fischer-Tropsch waxes with melting points between 100 and 115 C as well as polyethylene waxes with melting points between 85 and 140 C.
Suitable antioxidants and stabilizers include sterically hindered phenols and/or thioethers, sterically hindered aromatic amines and the like.
All known blowing agents, such as "chemical blowing agents" which liberate gases by decomposition or "physical blowing agents", i.e., expanding hollow beads (also sometimes referred to as expandable microspheres), are suitable as blowing agent in the present invention.
Mixtures of different blowing agents may be used to advantage; for example, a blowing agent having a relatively low activation temperature may be used in combination with a blowing agent having a relatively high activation temperature.
Examples of "chemical blowing agents" include azo, hydrazide, nitroso and carbazide compounds such as azobisisobutyronitrile, azodicarbonamide, di-nitroso-pentamethylenetetramine, 4,4'-oxybis(benzenesulfonic acid hydrazide), diphenyl-sulfone-3,3'-disulfohydrazide, benzene- 1,3 -disulfohydrazide and p-toluenesulfonyl semicarbazide.
Suitable rosin resins are abietic acid, levopimaric acid, neoabietic acid, dextropimaric acid, palustric acid, alkyl esters of the aforementioned rosin acids, and hydrogenation products of rosin acid derivatives.
Examples of suitable plasticizers include CI_10 alkyl esters of dibasic acids (e.g., phthalate esters), diaryl ethers, benzoates of polyalkylene glycols, organic phosphates, and alkylsulfonic acid esters of phenol or cresol.
Suitable waxes include paraffinic waxes having melting ranges from 45 to 70 C, microcrystalline waxes with melting ranges from 60 to 95 C, synthetic Fischer-Tropsch waxes with melting points between 100 and 115 C as well as polyethylene waxes with melting points between 85 and 140 C.
Suitable antioxidants and stabilizers include sterically hindered phenols and/or thioethers, sterically hindered aromatic amines and the like.
All known blowing agents, such as "chemical blowing agents" which liberate gases by decomposition or "physical blowing agents", i.e., expanding hollow beads (also sometimes referred to as expandable microspheres), are suitable as blowing agent in the present invention.
Mixtures of different blowing agents may be used to advantage; for example, a blowing agent having a relatively low activation temperature may be used in combination with a blowing agent having a relatively high activation temperature.
Examples of "chemical blowing agents" include azo, hydrazide, nitroso and carbazide compounds such as azobisisobutyronitrile, azodicarbonamide, di-nitroso-pentamethylenetetramine, 4,4'-oxybis(benzenesulfonic acid hydrazide), diphenyl-sulfone-3,3'-disulfohydrazide, benzene- 1,3 -disulfohydrazide and p-toluenesulfonyl semicarbazide.
"Chemical blowing agents" may benefit from the presence of additional activators such as zinc compounds (e.g., zinc oxide), (modified) ureas and the like.
However, "physical blowing agents" and particularly expandable hollow microbeads (sometimes referred to as microspheres) are also useable. Advantageously, the hollow microbeads are based on polyvinylidene chloride copolymers or acrylonitrile/ (meth)acrylate copolymers and contain encapsulated volatile substances such as light hydrocarbons or halogenated hydrocarbons.
Suitable expandable hollow microbeads are commercially available, e.g., under the trademarks "Dualite" and "Expancel" respectively, from Pierce & Stevens (now part of Henkel Corporation) or Akzo Nobel, respectively.
Suitable curing agents include substances capable of inducing free radical reactions, in particular organic peroxides including ketone peroxides, diacyl peroxides, peresters, perketals, hydroperoxides and others such as cumene hydroperoxide, bis(tert-butylperoxy) diisopropylbenzene, di(-2-tert-butyl peroxyisopropyl benzene), 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, dicumyl peroxide, t-butylperoxybenzoate, di-alkyl peroxydicarbonates, di-peroxyketals (such as 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane), ketone peroxides (e.g., methylethylketone peroxide), and 4,4- di-tert-butylperoxy n-butyl valerate. The curing agent is preferably a latent curing agent, that is, a curing agent that is essentially inert or non-reactive at room temperature but is activated by heating to an elevated temperature (for example, a temperature within the range of from about 130 degrees C to about 240 degrees C).
In a particularly desirable embodiment, the thermally expandable composition contains a small amount (e.g., 0.1 to 5 weight percent or 0.5 to 2 weight percent) of one or more olefinically unsaturated monomers and/or oligomers such as C1 to C6 alkyl (meth)acrylates (e.g., methyl acrylate), unsaturated carboxylic acids such as (meth)acrylic acid, unsaturated anhydrides such as maleic anhydride, (meth)acrylates of polyols and alkoxylated polyols such as glycerol triacrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA) and the like, triallyl trimesate, triallyl trimellitate (TATM), tetraallyl pyromellitate, the diallyl ester of 1,1,3,-trimethyl-5-carboxy-3-(4-carboxyphenyl)indene, dihydrodicyclo pentadienyl acrylate, trimethylolpropane trimellitate (TMPTM), pentaerythritol trimethacrylate, phenylene-dimaleimide, tri(2-acryloxyethyl)isocyanurate, triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), tri(2-methacryloxyethyl)trimellitate, unsaturated nitriles such as (meth)acrylonitrile, vinyl compounds (including vinyl aromatic compounds such as styrene), allyl compounds and the like and combinations thereof. In one embodiment, the olefinically unsaturated monomer(s) and/or oligomer(s) used contain only one carbon-carbon double bond per molecule (i.e., the monomer or oligomer is monofunctional with respect to olefinically unsaturated functional groups). Preferably, the monomer(s) and/or oligomer(s) are selected to be capable of undergoing free radical reaction (e.g., oligomerization or polymerization) initiated by the curing agent(s) present in the expandable material when the expandable material is heated to a temperature effective to activate the curing agent (for example, by thermal decomposition of a peroxide).
Examples of suitable fillers include ground and precipitated chalks, talc, calcium carbonate, carbon black, calcium-magnesium carbonates, and barite and silicate fillers of the aluminum-magnesium-calcium type, such as wollastonite and chlorite. Preferably, however, the total amount of filler is limited to less than 10% by weight, more preferably less than 5% by weight.
In one embodiment, the expandable material contains no filler (defined herein as substantially inorganic particles, such as particles of the materials mentioned above).
In certain embodiments of the invention, the components of the thermally expandable material are selected such that the expandable material is free or substantially free of any thermosettable resin such as an epoxy resin (e.g., the expandable material contains less than 5 % or less than 1%
by weight epoxy resin).
Expansion of the thermally expandable material is achieved by a heating step, wherein the thermally expandable material is heated for a time and at a temperature effective to activate the blowing agent and also any curing agent that may be present.
Depending on the nature of the thermally expandable material and the line conditions at the assembly line, the heating step is typically carried out at a temperature from 130 C to 240 C, preferably from 150 C to 200 C, with a residence time in the oven from about 10 min. to about min.
However, "physical blowing agents" and particularly expandable hollow microbeads (sometimes referred to as microspheres) are also useable. Advantageously, the hollow microbeads are based on polyvinylidene chloride copolymers or acrylonitrile/ (meth)acrylate copolymers and contain encapsulated volatile substances such as light hydrocarbons or halogenated hydrocarbons.
Suitable expandable hollow microbeads are commercially available, e.g., under the trademarks "Dualite" and "Expancel" respectively, from Pierce & Stevens (now part of Henkel Corporation) or Akzo Nobel, respectively.
Suitable curing agents include substances capable of inducing free radical reactions, in particular organic peroxides including ketone peroxides, diacyl peroxides, peresters, perketals, hydroperoxides and others such as cumene hydroperoxide, bis(tert-butylperoxy) diisopropylbenzene, di(-2-tert-butyl peroxyisopropyl benzene), 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, dicumyl peroxide, t-butylperoxybenzoate, di-alkyl peroxydicarbonates, di-peroxyketals (such as 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane), ketone peroxides (e.g., methylethylketone peroxide), and 4,4- di-tert-butylperoxy n-butyl valerate. The curing agent is preferably a latent curing agent, that is, a curing agent that is essentially inert or non-reactive at room temperature but is activated by heating to an elevated temperature (for example, a temperature within the range of from about 130 degrees C to about 240 degrees C).
In a particularly desirable embodiment, the thermally expandable composition contains a small amount (e.g., 0.1 to 5 weight percent or 0.5 to 2 weight percent) of one or more olefinically unsaturated monomers and/or oligomers such as C1 to C6 alkyl (meth)acrylates (e.g., methyl acrylate), unsaturated carboxylic acids such as (meth)acrylic acid, unsaturated anhydrides such as maleic anhydride, (meth)acrylates of polyols and alkoxylated polyols such as glycerol triacrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA) and the like, triallyl trimesate, triallyl trimellitate (TATM), tetraallyl pyromellitate, the diallyl ester of 1,1,3,-trimethyl-5-carboxy-3-(4-carboxyphenyl)indene, dihydrodicyclo pentadienyl acrylate, trimethylolpropane trimellitate (TMPTM), pentaerythritol trimethacrylate, phenylene-dimaleimide, tri(2-acryloxyethyl)isocyanurate, triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), tri(2-methacryloxyethyl)trimellitate, unsaturated nitriles such as (meth)acrylonitrile, vinyl compounds (including vinyl aromatic compounds such as styrene), allyl compounds and the like and combinations thereof. In one embodiment, the olefinically unsaturated monomer(s) and/or oligomer(s) used contain only one carbon-carbon double bond per molecule (i.e., the monomer or oligomer is monofunctional with respect to olefinically unsaturated functional groups). Preferably, the monomer(s) and/or oligomer(s) are selected to be capable of undergoing free radical reaction (e.g., oligomerization or polymerization) initiated by the curing agent(s) present in the expandable material when the expandable material is heated to a temperature effective to activate the curing agent (for example, by thermal decomposition of a peroxide).
Examples of suitable fillers include ground and precipitated chalks, talc, calcium carbonate, carbon black, calcium-magnesium carbonates, and barite and silicate fillers of the aluminum-magnesium-calcium type, such as wollastonite and chlorite. Preferably, however, the total amount of filler is limited to less than 10% by weight, more preferably less than 5% by weight.
In one embodiment, the expandable material contains no filler (defined herein as substantially inorganic particles, such as particles of the materials mentioned above).
In certain embodiments of the invention, the components of the thermally expandable material are selected such that the expandable material is free or substantially free of any thermosettable resin such as an epoxy resin (e.g., the expandable material contains less than 5 % or less than 1%
by weight epoxy resin).
Expansion of the thermally expandable material is achieved by a heating step, wherein the thermally expandable material is heated for a time and at a temperature effective to activate the blowing agent and also any curing agent that may be present.
Depending on the nature of the thermally expandable material and the line conditions at the assembly line, the heating step is typically carried out at a temperature from 130 C to 240 C, preferably from 150 C to 200 C, with a residence time in the oven from about 10 min. to about min.
It is advantageous to take benefit of the heating step that follows the passage of the vehicle parts in the generally used electro coating bath (E-coat bath) to cause expansion of the thermally expandable material as the temperature during this heating step is generally sufficient to cause the expected expansion.
While only selected embodiments have been chosen to illustrate the present invention, it will be apparent to those skilled in the art from this disclosure that various changes and modifications can be made herein without departing from the scope of the invention as defined in the appended claims. Furthermore, the foregoing description of the embodiments according to the present invention is provided for illustration only, and not for the purpose of limiting the invention as defined by the appended claims and their equivalents.
EXAMPLE
A thermally expandable material in accordance with the present invention is prepared by combining the following components:
45 parts by weight SIS block copolymer, styrene content 20%
5 parts by weight aromatic hydrocarbon resin tackifier 2.5 parts by weight diisononylphthalate 4.5 parts by weight microcrystalline wax 27.5 parts by weight thermoplastic ethylene/vinyl acetate copolymer (28% vinyl acetate) 0.1 parts by weight phenolic antioxidant 8.8 parts by weight blowing agent (azodicarbonamide) 1.0 part by weight 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane 0.5 parts by weight methyl acrylate 1.5 parts by weight zinc oxide treated urea The thermally expandable material thereby obtained may be expanded by heating at a temperature of 180 degrees C for 20 minutes to provide an expanded (foamed) material useful 5 for reducing the transfer of vibrations generated by a vibration generator.
While only selected embodiments have been chosen to illustrate the present invention, it will be apparent to those skilled in the art from this disclosure that various changes and modifications can be made herein without departing from the scope of the invention as defined in the appended claims. Furthermore, the foregoing description of the embodiments according to the present invention is provided for illustration only, and not for the purpose of limiting the invention as defined by the appended claims and their equivalents.
EXAMPLE
A thermally expandable material in accordance with the present invention is prepared by combining the following components:
45 parts by weight SIS block copolymer, styrene content 20%
5 parts by weight aromatic hydrocarbon resin tackifier 2.5 parts by weight diisononylphthalate 4.5 parts by weight microcrystalline wax 27.5 parts by weight thermoplastic ethylene/vinyl acetate copolymer (28% vinyl acetate) 0.1 parts by weight phenolic antioxidant 8.8 parts by weight blowing agent (azodicarbonamide) 1.0 part by weight 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane 0.5 parts by weight methyl acrylate 1.5 parts by weight zinc oxide treated urea The thermally expandable material thereby obtained may be expanded by heating at a temperature of 180 degrees C for 20 minutes to provide an expanded (foamed) material useful 5 for reducing the transfer of vibrations generated by a vibration generator.
Claims (20)
1. A thermally expandable material that when expanded has a Young's storage modulus E' between 0.1 MPa and 1000 MPa and a loss factor higher than 0.3 at a temperature between -10 and +40 degrees C in the frequency range 0 to 500 Hz.
2. A thermally expandable material in accordance with Claim 1, wherein said thermally expandable material comprises at least one thermoplastic elastomer, at least one non-elastomeric thermoplastic, at least one stabilizer or antioxidant, at least one blowing agent, and at least one curing agent.
3. A thermally expandable material in accordance with Claim 1 or Claim 2, wherein said thermally expandable material is comprised of at least one peroxide curing agent.
4. A thermally expandable material in accordance with any of Claims 1 to 3, wherein said thermally expandable material is comprised of at least one thermoplastic elastomer selected from the group consisting of thermoplastic polyurethanes, styrene/butadiene block copolymers, hydrogenated styrene/butadiene block copolymers, styrene/isoprene block copolymers, and hydrogenated styrene/isoprene block copolymers.
5. A thermally expandable material in accordance with any of Claims 1 to 4, wherein said thermally expandable material is comprised of at least one non-elastomeric thermoplastic selected from the group consisting of ethylene/vinyl acetate copolymers and ethylene/methyl acrylate copolymers.
6. A thermally expandable material in accordance with any of Claims 1 to 5, wherein said thermally expandable material is comprised of at least one non-elastomeric thermoplastic selected from the group consisting of ethylene/vinyl acetate copolymers and ethylene/methyl acrylate copolymers and at least one thermoplastic elastomer selected from the group consisting of thermoplastic polyurethanes, styrene/butadiene block copolymers, hydrogenated styrene/butadiene block copolymers, styrene/isoprene block copolymers, and hydrogenated styrene/isoprene block copolymers.
7. A thermally expandable material in accordance with any of Claims 1 to 6, wherein said thermally expandable material contains less than 10 weight percent filler.
8. A thermally expandable material in accordance with any of Claims 1 to 7, wherein said thermally expandable material is comprised of at least one olefinically unsaturated monomer or oligomer.
9. A thermally expandable material in accordance with any of Claims 1 to 8, wherein said thermally expandable material is comprised of at least one C1 to C6 alkyl (meth)acrylate.
10. A thermally expandable material in accordance with any of Claims 1 to 9, wherein said thermally expandable material is comprised of at least one plasticizer.
11. A thermally expandable material in accordance with any of Claims 1 to 10, wherein said thermally expandable material is comprised of at least one wax.
12. A thermally expandable material in accordance with any of Claims 1 to 11, wherein said thermally expandable material is comprised of at least one latent chemical blowing agent.
13. A thermally expandable material in accordance with any of Claims 1 to 12, wherein said thermally expandable material is comprised of at least one tackifying resin.
14. A thermally expandable material in accordance with any of Claims 1 to 13, wherein said thermally expandable material is comprised of at least one blowing agent activator.
15. A thermally expandable material in accordance with any of Claims 1 to 14, wherein said thermally expandable material is comprised of at least one olefinically unsaturated monomer or oligomer having only one carbon-carbon double bond per molecule.
16. A thermally expandable material in accordance with any of Claims 1 to 15, wherein said thermally expandable material is comprised of at least one styrene/isoprene/styrene triblock polymer or fully or partially hydrogenated derivative thereof with at least about 50% of the polymerized isoprene monomer moieties having 1,2 and/or 3,4 configurations.
17. A thermally expandable material in accordance with Claim 1, wherein said thermally expandable material comprises:
a). from 25 to 70% by weight of at least one thermoplastic elastomer;
b). from 15 to 40% by weight of at least one non-elastomeric thermoplastic;
c). from 0.01 to 2% by weight of at least one stabilizer or antioxidant;
d). from 2 to 15% by weight of at least one blowing agent; and e). from 0.5 to 4% by weight of at least one curing agent.
a). from 25 to 70% by weight of at least one thermoplastic elastomer;
b). from 15 to 40% by weight of at least one non-elastomeric thermoplastic;
c). from 0.01 to 2% by weight of at least one stabilizer or antioxidant;
d). from 2 to 15% by weight of at least one blowing agent; and e). from 0.5 to 4% by weight of at least one curing agent.
18. A thermally expandable material in accordance with Claim 1, wherein said thermally expandable material comprises:
a). from 35 to 55% by weight of at least one thermoplastic elastomer selected from the group consisting of thermoplastic polyurethanes, styrene/butadiene block copolymers, hydrogenated styrene/butadiene block copolymers, styrene/isoprene block copolymers, and hydrogenated styrene/isoprene block copolymers;
b). from 20 to 35% by weight of at least one non-elastomeric thermoplastic selected from the group consisting of ethylene/vinyl acetate copolymers and ethylene/methyl acrylate copolymers;
c). from 0.05 to 1% by weight of at least one stabilizer or antioxidant;
d). at least one latent chemical blowing agent in an amount effective to cause the expandable material to expand at least 100% in volume when heated at a temperature of 150 degrees C for at least 20 minutes;
e). from 0.5 to 4% by weight of at least one peroxide; and f). from 0.5 to 2% by weight of at least one olefinically unsaturated monomer or oligomer;
a). from 35 to 55% by weight of at least one thermoplastic elastomer selected from the group consisting of thermoplastic polyurethanes, styrene/butadiene block copolymers, hydrogenated styrene/butadiene block copolymers, styrene/isoprene block copolymers, and hydrogenated styrene/isoprene block copolymers;
b). from 20 to 35% by weight of at least one non-elastomeric thermoplastic selected from the group consisting of ethylene/vinyl acetate copolymers and ethylene/methyl acrylate copolymers;
c). from 0.05 to 1% by weight of at least one stabilizer or antioxidant;
d). at least one latent chemical blowing agent in an amount effective to cause the expandable material to expand at least 100% in volume when heated at a temperature of 150 degrees C for at least 20 minutes;
e). from 0.5 to 4% by weight of at least one peroxide; and f). from 0.5 to 2% by weight of at least one olefinically unsaturated monomer or oligomer;
19 wherein said thermally expandable material contains less than 10% by weight filler.
19. A thermally expandable material in accordance with Claim 1, wherein said thermally expandable material comprises:
a). from 25 to 70% by weight of at least one thermoplastic elastomer;
b). from 15 to 40% by weight of at least one non-elastomeric thermoplastic;
c). from 0.01 to 2% by weight of at least one stabilizer or antioxidant;
d). from 2 to 15% by weight of at least one blowing agent;
e). from 0.5 to 4% by weight of at least one curing agent;
f). at least one tackifying resin, in an amount up to 10% by weight;
g). at least one wax, in an amount up to 10% by weight; and h). at least one plasticizer, in an amount up to 5% by weight.
19. A thermally expandable material in accordance with Claim 1, wherein said thermally expandable material comprises:
a). from 25 to 70% by weight of at least one thermoplastic elastomer;
b). from 15 to 40% by weight of at least one non-elastomeric thermoplastic;
c). from 0.01 to 2% by weight of at least one stabilizer or antioxidant;
d). from 2 to 15% by weight of at least one blowing agent;
e). from 0.5 to 4% by weight of at least one curing agent;
f). at least one tackifying resin, in an amount up to 10% by weight;
g). at least one wax, in an amount up to 10% by weight; and h). at least one plasticizer, in an amount up to 5% by weight.
20. A thermally expandable material in accordance with Claim 1, wherein said thermally expandable material comprises:
a). from 35 to 55% by weight of at least one styrene/isoprene block copolymer thermoplastic elastomer selected from the group consisting of styrene/isoprene block copolymers;
b). from 20 to 35% by weight of at least one non-elastomeric thermoplastic selected from the group consisting of ethylene/vinyl acetate copolymers;
c). from 0.05 to 1% by weight of at least one stabilizer or antioxidant;
d). at least one latent chemical blowing agent in an amount effective to cause the expandable material to expand at least 100% in volume when heated at a temperature of 150 degrees C for at least 20 minutes;
e). from 0.5 to 4% by weight of at least one organic peroxide;
f). from 0.5 to 2% by weight of at least one C1 to C6 alkyl (meth)acrylate;
g). at least one tackifying resin, in an amount up to 10% by weight;
h). at least one plasticizer, in an amount up to 5% by weight; and i). at least one wax, in an amount up to 10% by weight;
wherein said thermally expandable material contains less than 10% by weight filler.
a). from 35 to 55% by weight of at least one styrene/isoprene block copolymer thermoplastic elastomer selected from the group consisting of styrene/isoprene block copolymers;
b). from 20 to 35% by weight of at least one non-elastomeric thermoplastic selected from the group consisting of ethylene/vinyl acetate copolymers;
c). from 0.05 to 1% by weight of at least one stabilizer or antioxidant;
d). at least one latent chemical blowing agent in an amount effective to cause the expandable material to expand at least 100% in volume when heated at a temperature of 150 degrees C for at least 20 minutes;
e). from 0.5 to 4% by weight of at least one organic peroxide;
f). from 0.5 to 2% by weight of at least one C1 to C6 alkyl (meth)acrylate;
g). at least one tackifying resin, in an amount up to 10% by weight;
h). at least one plasticizer, in an amount up to 5% by weight; and i). at least one wax, in an amount up to 10% by weight;
wherein said thermally expandable material contains less than 10% by weight filler.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP05292082.4A EP1772480B1 (en) | 2005-10-06 | 2005-10-06 | Reduction of transfer of vibrations |
| EP05292082.4 | 2005-10-06 | ||
| PCT/EP2006/009666 WO2007039309A1 (en) | 2005-10-06 | 2006-10-06 | High damping expandable material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2624332A1 true CA2624332A1 (en) | 2007-04-12 |
Family
ID=35998524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002624332A Abandoned CA2624332A1 (en) | 2005-10-06 | 2006-10-06 | High damping expandable material |
Country Status (12)
| Country | Link |
|---|---|
| US (2) | US7364221B2 (en) |
| EP (2) | EP1772480B1 (en) |
| JP (1) | JP5133250B2 (en) |
| KR (1) | KR101277485B1 (en) |
| CN (2) | CN101341198B (en) |
| AT (1) | ATE526356T1 (en) |
| BR (1) | BRPI0616990A2 (en) |
| CA (1) | CA2624332A1 (en) |
| ES (2) | ES2449515T3 (en) |
| MX (1) | MX2008004446A (en) |
| PL (1) | PL1940927T3 (en) |
| WO (2) | WO2007039309A1 (en) |
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| KR100726276B1 (en) | 2003-06-27 | 2007-06-08 | 미쓰이 가가쿠 가부시키가이샤 | Resin composition for foam and use thereof |
| JP4259295B2 (en) | 2003-09-29 | 2009-04-30 | Ｊｓｒ株式会社 | Hydrogenated diene copolymer, polymer composition, and molded article using the polymer composition |
| CA2550763A1 (en) | 2003-12-24 | 2005-07-21 | Bharat I. Chaudhary | Rheology modification of polymers |
| KR100703351B1 (en) * | 2004-05-06 | 2007-04-03 | 삼성전자주식회사 | Swing-type portable telephone |
| WO2006096531A1 (en) | 2005-03-04 | 2006-09-14 | Denovus Llc | Variable density foam |
| EP1772480B1 (en) * | 2005-10-06 | 2013-12-04 | Henkel AG & Co. KGaA | Reduction of transfer of vibrations |
-
2005
- 2005-10-06 EP EP05292082.4A patent/EP1772480B1/en active Active
- 2005-10-06 ES ES05292082.4T patent/ES2449515T3/en active Active
-
2006
- 2006-10-02 US US11/542,928 patent/US7364221B2/en active Active
- 2006-10-06 PL PL06806075T patent/PL1940927T3/en unknown
- 2006-10-06 CN CN2006800368055A patent/CN101341198B/en not_active Expired - Fee Related
- 2006-10-06 ES ES06806075T patent/ES2374645T3/en active Active
- 2006-10-06 CA CA002624332A patent/CA2624332A1/en not_active Abandoned
- 2006-10-06 EP EP06806075A patent/EP1940927B1/en active Active
- 2006-10-06 JP JP2008533942A patent/JP5133250B2/en not_active Expired - Fee Related
- 2006-10-06 KR KR1020087010399A patent/KR101277485B1/en not_active IP Right Cessation
- 2006-10-06 AT AT06806075T patent/ATE526356T1/en not_active IP Right Cessation
- 2006-10-06 CN CN2006800461016A patent/CN101341199B/en not_active Expired - Fee Related
- 2006-10-06 MX MX2008004446A patent/MX2008004446A/en active IP Right Grant
- 2006-10-06 WO PCT/EP2006/009666 patent/WO2007039309A1/en active Application Filing
- 2006-10-06 WO PCT/EP2006/009665 patent/WO2007039308A1/en active Application Filing
- 2006-10-06 BR BRPI0616990-2A patent/BRPI0616990A2/en not_active IP Right Cessation
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2008
- 2008-03-17 US US12/049,535 patent/US20080176969A1/en not_active Abandoned
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8372912B2 (en) | 2005-08-12 | 2013-02-12 | Eastman Chemical Company | Polyvinyl chloride compositions |
| US9388293B2 (en) | 2005-08-12 | 2016-07-12 | Eastman Chemical Company | Polyvinyl chloride compositions |
| US8088854B2 (en) | 2006-08-30 | 2012-01-03 | Eastman Chemical Company | Terephthalates as plasticizers in vinyl acetate polymer compositions |
| US8784989B2 (en) | 2006-08-30 | 2014-07-22 | Eastman Chemical Company | Sealant compositions having a novel plasticizer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5133250B2 (en) | 2013-01-30 |
| WO2007039308A1 (en) | 2007-04-12 |
| ES2374645T3 (en) | 2012-02-20 |
| CN101341198A (en) | 2009-01-07 |
| ATE526356T1 (en) | 2011-10-15 |
| BRPI0616990A2 (en) | 2011-07-05 |
| PL1940927T3 (en) | 2012-06-29 |
| US20070100060A1 (en) | 2007-05-03 |
| ES2449515T3 (en) | 2014-03-20 |
| CN101341199A (en) | 2009-01-07 |
| KR101277485B1 (en) | 2013-06-21 |
| MX2008004446A (en) | 2008-10-20 |
| EP1772480B1 (en) | 2013-12-04 |
| EP1940927B1 (en) | 2011-09-28 |
| EP1940927A1 (en) | 2008-07-09 |
| US7364221B2 (en) | 2008-04-29 |
| EP1772480A1 (en) | 2007-04-11 |
| WO2007039309A1 (en) | 2007-04-12 |
| CN101341198B (en) | 2011-07-27 |
| CN101341199B (en) | 2012-03-28 |
| JP2009510241A (en) | 2009-03-12 |
| KR20080077099A (en) | 2008-08-21 |
| US20080176969A1 (en) | 2008-07-24 |
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| EEER | Examination request | ||
| FZDE | Discontinued |
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